EP1299313B1 - Verfahren zur debrominierung von wässrigen salzlösungen durch ozon - Google Patents

Verfahren zur debrominierung von wässrigen salzlösungen durch ozon Download PDF

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Publication number
EP1299313B1
EP1299313B1 EP01969373A EP01969373A EP1299313B1 EP 1299313 B1 EP1299313 B1 EP 1299313B1 EP 01969373 A EP01969373 A EP 01969373A EP 01969373 A EP01969373 A EP 01969373A EP 1299313 B1 EP1299313 B1 EP 1299313B1
Authority
EP
European Patent Office
Prior art keywords
process according
concentrated aqueous
ozone
alkali metal
solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP01969373A
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English (en)
French (fr)
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EP1299313A1 (de
Inventor
Andreas Klingenberg
Manfred Klass
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Honeywell Specialty Chemicals Seelze GmbH
Original Assignee
Honeywell Specialty Chemicals Seelze GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Honeywell Specialty Chemicals Seelze GmbH filed Critical Honeywell Specialty Chemicals Seelze GmbH
Publication of EP1299313A1 publication Critical patent/EP1299313A1/de
Application granted granted Critical
Publication of EP1299313B1 publication Critical patent/EP1299313B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/10—Preparation of ozone
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K33/00—Medicinal preparations containing inorganic active ingredients
    • A61K33/40—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D3/00—Halides of sodium, potassium or alkali metals in general
    • C01D3/14—Purification
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F5/00—Compounds of magnesium
    • C01F5/26—Magnesium halides
    • C01F5/30—Chlorides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/12—Halogens or halogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/02—Non-contaminated water, e.g. for industrial water supply
    • C02F2103/026—Treating water for medical or cosmetic purposes

Definitions

  • the present invention relates to a process for the debromination of a salt solution containing impurities of bromide by the use of ozone.
  • bromide-containing chemicals are used in the pharmaceutical area, the purity requirements of the relevant pharmacopoeiae (Pharma Euro III, p. 1234-1235) are taken as a basis.
  • Compounds which are important in the present context are, for example, alkali and earth alkali compounds.
  • a process for the reduction of the bromide content by means of which the above-mentioned all-over bromide content of a compound can be achieved is, for example, embodied by the introduction of gaseous chlorine into a solution of the particular compound present in a suitable solvent, as for example water.
  • the publication DE-A 21 18 623 discloses a process for the purification of aqueous magnesium chloride solutions in which the bromide content is reduced by introducing chlorine gas into these solutions.
  • the present invention relates to a process for the debromination of a concentrated aqueous alkali metal chloride and/or earth alkali metal chloride solution containing impurities of bromide, in which the solution is contacted with ozone and the bromine thus formed, as well as excess ozone, are separated from the,aqueous solution.
  • the present invention relates to a process characterized in that concentrated aqueous solution contains the alkali metal and/or earth alkali metal chloride in an amount of preferred > 15 wt.-%, more preferred > 30 wt.-%, even more preferred > 50 wt.-%, most preferred > 65 wt.-%, with crystalline chloride salt taken as a basis for the calculation.
  • alkali metal and/or earth alkali metal chloride content as used in the process according to the invention is > 25 wt.-%, more preferred > 30 wt.-%, even more preferred > 50 wt.-% and particularly > 65 wt.-%, respectively calculated as crystalline chloride salt.
  • the solutions of which are treated by the process according to the invention in order to achieve debromination are concentrated aqueous magnesium chloride (MgCl 2 -6-H 2 0) solutions which serve as basic solutions for the crystallization of MgCl 2 -6-H 2 O according to Ph. Eur. 3 rd , which allows for a bromine content in the crystalline body which amounts to a maximum of 500 ppm.
  • MgCl 2 -6-H 2 0 concentrated aqueous magnesium chloride
  • the present invention also relates to a process characterized in that the concentrated aqueous solution is a concentrated aqueous magnesium chloride solution.
  • the content of one or more bromide impurity/impurities in the concentrated aqueous magnesium chloride solution lies in the range of > 100 ppm, more preferred in the range of > 1.000 ppm, and most preferred in the range of 1.000 to 4.000 ppm, in relation to solid MgCl 2 -6-H 2 O.
  • the present invention also relates to a process which is characterized in that the concentrated aqueous solution is a concentrated aqueous solution of MgCl 2 -6-H 2 0 having a content of one or more bromide impurity/impurities derived from the processing of carnallitic kali raw salts.
  • the ozone is produced from oxygen in situ using an ozone generating device with the oxygen or air enriched in oxygen being passed through the concentrated aqueous solution in a mixture with ozone.
  • concentration ozone in the gaseous oxygen or in the air enriched in gaseous oxygen lies in the range of 1 to 25 vol.-%, preferred in the range of 5 to 15 vol.-%.
  • the admission of oxygen or air enriched in oxygen to the solution amounts to 103 l/h or 51.6 l/h, respectively, for a laboratory scale setup, with an industrial scale setup being possibly designed for e.g. 1 Nm 3 /h.
  • the mass ratio of absorbed ozone to oxidized bromide desirably lies in the range of about 0.2 to 0.6 : 1, which corresponds to a molar ratio of about 0.3 to 0.75 : 1.
  • the pH value of the starting solution in the process according to the invention generally lies in the range of 6 ⁇ 1, which corresponds to a pH value of 8 to 9 at a dilution of 1 to 10.
  • magnesium chloride which has a bromide content being ⁇ 500 ppm, preferred ⁇ 250 ppm, in relation to crystalline magnesium chloride.
  • magnesium chloride is obtained in which bromide is not detectable any more.
  • the temperature at which the process according to the invention is carried out lies usually in the range of about 0°C to 80°C, preferred in the range of 25 ⁇ 10°C.
  • a further advantage of the process according to the invention is embodied by the fact that bromate eventually formed may undergo comproportionation with bromide to bromine which is removed according to the invention.
  • the bromine formed by oxidation during the course of the process may be removed from the solution according to all processes known in the state of the art.
  • the bromine formed during the debromination process by oxidation using ozone is expelled together with excess ozone using the stream of oxygen gas or the air enriched in oxygen gas.
  • the volume stream is highly dependent on the scale of the plant.
  • Oxygen or air enriched in oxygen is blown into the solution with a turnover of generally 10 to 200 l/h, preferred 50 to 150 l/h (laboratory experiment); 0.1 to 10 m 3 /h, preferred 1 to 5 m 3 /h (6.000 l reactor); and 1 to 50 m 3 /h, preferred 5 to 20 m 3 /h (40.000 l reactor).
  • the bromine expelled by the exhaust gas is washed out in an exhaust gas washing device, which, for example, may be run using a thiosulfate solution.
  • the present invention in its most general embodiment relates to the use of ozone in a process for the debromination of a concentrated aqueous alkali metal and/or earth alkali metal chloride solution containing impurities of bromide, in particular magnesium chloride solution, in which the solution is contacted with ozone and bromine thus formed as well as excess ozone, is removed from the aqueous solution.
  • the present invention relates to the use of magnesium chloride having a bromide content of ⁇ 250 ppm, in relation to crystalline magnesium chloride, which is manufactured according to the process according to the invention by subsequent crystallization of the magnesium chloride solution, to be used for medical purposes.
  • the highly pure magnesium chloride is preferred employed for the manufacture of hemodialysis, hemofiltration or peritoneal dialysis solutions and for parenteral applications, in particular for infusion solutions.
  • the present invention also relates to the use of magnesium chloride as specified above for the production of pharmaceuticals, particularly for the production of an aqueous solution for dialysis purposes.
  • the remaining bromide content of the solution was determined in time intervals of 5 or 15 minutes, respectively, as well as the ozone content in the feed gas stream and the off gas stream. Furthermore, the bromate content of the debrominated solution was determined by ion chromatography.
  • Example 2 Example 3 free acid (HCl) calculated as solid content 0.005 % --- --- free alkali (NaOH) calculated as solid content --- 0.008 % 0.008 % amount of gas/ ozone content 103 l/h 13 % 103 l/h 13 % 51.6 l/h 14.5 % bromide content of the starting solution (calculated as solid content in relation to MgCl 2 -6-H 2 O) 0.13 % 0.13 % 0.13 % reaction time (bromide ⁇ 500 ppm) 25 min. 25 min. 35 min. reaction time (bromide not detectable) 45 min. 55 min. 45 min.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Epidemiology (AREA)
  • Public Health (AREA)
  • Medicinal Chemistry (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Geology (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Veterinary Medicine (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Claims (18)

  1. Verfahren zum Entbromen einer konzentrierten wässrigen, Bromid-Verunreinigung enthaltenden Alkalimetall- und/oder Erdalkalimetallchlorid-Lösung, worin man die Lösung mit Ozon in Kontakt bring und entstandenes Brom sowie überschüssiges Ozon aus der wässrigen Lösung abtrennt.
  2. Verfahren nach Anspruch 1, worin der Gehalt der konzentrierten wässrigen Lösung an Alkalimetall- und/oder Erdalkalimetallchlorid > 30 Gew.-% beträgt, berechnet als kristallines Chloridsalz.
  3. Verfahren nach Anspruch 2, worin der Gehalt an Alkalimetall- und/oder Erdalkalimetallchlorid > 50 Gew.-% beträgt, berechnet als kristallines Chloridsalz.
  4. Verfahren nach Anspruch 3, worin der Gehalt an Alkalimetall- und/oder Erdalkalimetallchlorid > 65 Gew.-% beträgt, berechnet als kristallines Chloridsalz.
  5. Verfahren nach einem oder mehreren Ansprüchen 1 bis 4, worin die konzentrierte wässrige Lösung eine konzentrierte wässrige Magnesiumchloridlösung ist.
  6. Verfahren nach Anspruch 5, worin die konzentrierte wässrige Lösung eine konzentrierte wässrige Magnesiumchlorid-Lösung mit einem Gehalt an einer oder mehreren Bromid-Verunreinigung(en) im Bereich von > 100 ppm, ist bezogen auf festes MgCl2.
  7. Verfahren nach Anspruch 6, worin die konzentrierte wässrige Lösung eine konzentrierte wässrige Magnesiumchlorid-Lösung mit einem Gehalt an einer oder mehreren Bromid-Verunreinigung(en) im Bereich von > 1.000 ppm ist, bezogen auf festes MgCl2.
  8. Verfahren nach Anspruch 7, worin die konzentrierte wässrige Lösung eine konzentrierte wässrige Magnesiumchlorid-Lösung mit einem Gehalt an einer oder mehreren Bromid-Verunreinigung(en) im Bereich von 1.000 bis 4.000 ppm ist, bezogen auf festes MgCl2.
  9. Verfahren nach einem oder mehreren der Ansprüche 1 bis 8, worin die wässrige Lösung eine konzentrierte wässrige Lösung von MgC12 mit einem Gehalt an einer oder mehreren Bromid-Verunreinigung(en) aus der Verarbeitung carnallitischer Kalirohsalze ist.
  10. Verfahren nach einem oder mehreren der Ansprüche 1 bis 9, worin das Ozon in situ aus Sauerstoff erzeugt wird.
  11. Verfahren nach Anspruch 10, worin das Ozon in situ aus Sauerstoff erzeugt wird, der durch die konzentrierte wässrige Lösung geleitet wird, bevorzugt in situ aus Sauerstoff erzeugt wird, der in Form von Sauerstoffgas oder mit Sauerstoffgas angereicherter Luft durch die konzentrierte wässrige Lösung geleitet wird.
  12. Verfahren nach Anspruch 11, worin die Konzentration des Ozons in dem Sauerstoffgas oder in der mit Sauerstoffgas angereicherten Luft im Bereich von 1 bis 25 Vol.-% liegt, bevorzugt im Bereich von 5 bis 15 Vol.-%.
  13. Verfahren nach einem oder mehreren der Ansprüche 1 bis 12, worin der pH-Wert im Bereich von 6 ± 1 liegt.
  14. Verfahren nach einem oder mehreren der Ansprüche 1 bis 13, worin Magnesiumchlorid mit einem Br-Gehalt von < 500 ppm hergestellt wird, bezogen auf kristallines Magnesiumchlorid.
  15. Verfahren nach Anspruch 14, worin Magnesiumchlorid mit einem Br-Gehalt von < 250 ppm, hergestellt wird, bezogen auf kristallines Magnesiumchlorid.
  16. Verfahren nach einem oder mehreren der Ansprüche 1 bis 15, welches bei 25 °C ± 10 °C durchgeführt wird.
  17. Verfahren nach einem oder mehreren der Ansprüche 1 bis 16, worin das im Rahmen der Oxidation von Bromid mit Ozon entstandene Brom zusammen mit überschüssigem Ozon mit dem Sauerstoffstrom bzw. Luft/Sauerstoffstrom aus der konzentrierten wässrigen Lösung ausgetrieben und gegebenenfalls in einem Abgaswäscher ausgewaschen wird.
  18. Verwendung von Ozon zum Entbromen einer konzentrierten wässrigen, eine oder mehrere Bromid-Verunreinigung(en) enthaltenden Alkalimetall und/oder Erdalkalimetallchlorid-Lösung, insbesondere Magnesiumchlorid-Lösung, gemäß dem Verfahren nach Anspruch 1, die bei der Herstellung von Arzneimittel verwendet wird.
EP01969373A 2000-07-12 2001-07-12 Verfahren zur debrominierung von wässrigen salzlösungen durch ozon Expired - Lifetime EP1299313B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10033762A DE10033762A1 (de) 2000-07-12 2000-07-12 Verfahren zum Entbromen einer wäßrigen Salzlösung unter Verwendung von Ozon
DE10033762 2000-07-12
PCT/EP2001/008063 WO2002004363A1 (en) 2000-07-12 2001-07-12 Process for the debromination of an aqueous salt solution using ozone

Publications (2)

Publication Number Publication Date
EP1299313A1 EP1299313A1 (de) 2003-04-09
EP1299313B1 true EP1299313B1 (de) 2004-04-21

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Application Number Title Priority Date Filing Date
EP01969373A Expired - Lifetime EP1299313B1 (de) 2000-07-12 2001-07-12 Verfahren zur debrominierung von wässrigen salzlösungen durch ozon

Country Status (8)

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US (1) US20040020864A1 (de)
EP (1) EP1299313B1 (de)
AT (1) ATE264815T1 (de)
AU (1) AU2001289646A1 (de)
BR (1) BR0112464A (de)
CA (1) CA2413018A1 (de)
DE (2) DE10033762A1 (de)
WO (1) WO2002004363A1 (de)

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4447405A (en) * 1982-08-26 1984-05-08 Koppers Company, Inc. Removal of bromides from arsenic acid solution
DE4428147A1 (de) * 1994-08-09 1996-02-15 Bwt Wassertechnik Gmbh Verfahren und Vorrichtung zur Trinkwasseraufbereitung
US6024882A (en) * 1997-08-08 2000-02-15 Applied Process Technology, Inc. Process and apparatus for water decontamination
DE19830130B4 (de) * 1998-07-06 2007-01-18 Robert Bosch Gmbh Schaltungsanordnung für eine PLL-Schaltung (Phase-locked-Loop) zur Frequenzvervielfachung
DE19830310A1 (de) * 1998-07-07 2000-01-13 Riedel De Haen Gmbh Verfahren zur Abreicherung des Bromidgehaltes aus einer wäßrigen Bromid enthaltenden Lösung unter Verwendung von Wasserstoffperoxid
US5980854A (en) * 1998-09-23 1999-11-09 Noranda, Inc. Method for the production of a magnesium chloride solution

Also Published As

Publication number Publication date
AU2001289646A1 (en) 2002-01-21
DE10033762A1 (de) 2002-01-31
CA2413018A1 (en) 2002-01-17
US20040020864A1 (en) 2004-02-05
EP1299313A1 (de) 2003-04-09
DE60102927D1 (de) 2004-05-27
BR0112464A (pt) 2003-07-22
ATE264815T1 (de) 2004-05-15
WO2002004363A1 (en) 2002-01-17

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